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Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
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D1319 − 20a
FIG. 1 Adsorption Columns with Standard Wall (left) and Precision Bore (right) Tubing in Analyzer Section
the length of an approximately 100 mm thread of mercury shall the internal geometry is essentially similar to the aforemen-
not vary by more than 0.3 mm in any part of the analyzer tioned procedure and provides for a smooth physical transition
section. In glass-sealing the various sections to each other, from the inner diameters of the two glass column sections.
long-taper connections shall be made instead of shouldered Similar commercial compression-type connectors may be em-
connections. Support the silica gel with a small piece of glass ployed at the terminal end of the 3 mm analyzer section, having
wool located between the ball and socket of the 12/2 spherical an integral porous support to retain the silica gel.
joint and covering the analyzer outlet. The column tip attached 6.1.2 For convenience, adsorption columns with standard
to the 12/2 socket shall have a 2 mm internal diameter. Clamp wall tubing, as shown on the left in Fig. 1, can be used. When
the ball and socket together and ensure that the tip does not using standard wall tubing for the analyzer section, it is
tend to slide from a position in a direct line with the analyzer necessary to select tubing of uniform bore and to provide a
section during the packing and subsequent use of the column. leakproof connection between the separator and the analyzer
Commercial compression-type connectors may be used to sections. Calibrations of standard wall tubing would be im-
couple the bottom of the separator section (which has been cut practical; however, any variations of 0.5 mm or greater, as
square), to the disposable 3 mm analyzer section, provided that measured by ordinary calipers, in the outside diameter along
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D1319 − 20a
TABLE 1 Tolerance Limits to Column Dimensions 5 mm length of vinyl tubing has been found to be suitable. To
Standard Column Dimensions ensure a leakproof glass-to-vinyl seal with the analyzer section,
Charger Section it is necessary to heat the upper end of the analyzer section
Inside diameter = 12 mm ± 2 mm
Pack gel to this level = approximately 75 mm until it is just hot enough to melt the vinyl, then insert the upper
Overall length = 150 mm ± 5 mm end of the analyzer section into the vinyl sleeve. Alternatively,
Neck Section this seal can be made by securing the vinyl sleeve to the
Inside diameter = 2 mm ± 0.5 mm
Overall length = 50 mm ± 5 mm analyzer section by wrapping it tightly with soft wire. Com-
Separator Section mercial compression-type connectors may be used to couple
Inside diameter = 5 mm ± 0.5 mm the bottom of the separator section (which has been cut
Overall length = 190 mm ± 5 mm
Long taper section below separator square), to the 3 mm analyzer section, provided that the
Tip outside diameter = 3.5 mm ± 0.5 mm internal geometry is essentially similar to the aforementioned
Tip inside diameter = 2 mm ± 0.5 mm procedure and provides for a smooth physical transition from
Overall length = 25 mm ± 2 mm
Analyzer Section the inner diameters of the two glass column sections. Similar
Inside diameter = 1.5 mm ± 0.5 mm commercial compression-type connectors may be employed at
Standard wall tubing
Overall length = 1200 mm ± 30 mm
the terminal end of the 3 mm analyzer section having an
Precision Bore Column Dimensions integral porous support to retain the silica gel.
Charger section 6.1.3 An alternative pressuring gas connection is shown in
Inside diameter = 12 mm ± 2 mm
Pack gel to this level = approximately 75 mm
Fig. 2. Otherwise, all adsorption column dimensions and
Overall length = 150 mm ± 5 mm requirements are unchanged.
Neck Section
Inside diameter = 2 mm ± 0.5 mm 6.2 Zone-Measuring Device—The zones may be marked
Overall length = 50 mm ± 5 mm with a glass-writing pencil and the distances measured with a
Separator Section meter rule, with the analyzer section lying horizontally.
Inside diameter = 5 mm ± 0.5 mm
Overall length = 190 mm ± 5 mm Alternatively, the meter rule may be fastened adjacent to the
Analyzer Section column. In this case, it is convenient to have each rule fitted
Inside diameter = 1.60 mm -1.65 mm
with four movable metal index clips (Fig. 1) for marking zone
Overall length = 1200 mm ± 30 mm
Tip boundaries and measuring the length of each zone.
Overall length = 30 mm ± 5 mm
6.3 Ultraviolet Light Source, with radiation predominantly
at 365 nm is required. A convenient arrangement consists of
one or two 915 mm or 1220 mm units mounted vertically along
the tube can be taken as an indication of irregularities in the the apparatus. Adjust to give the best fluorescence.
inner diameter and such tubing should not be used. Prepare the
glassware to retain the gel. One way to accomplish this is to 6.4 Electric Vibrator, for vibrating individual columns or the
draw out one end of the tubing selected for the analyzer section frame supporting multiple columns.
to a fine capillary. Connect the other end of the analyzer section 6.5 Hypodermic Syringe, 1 mL, graduated to 0.01 mL or
to the separator section with a suitable length of vinyl tubing, 0.02 mL, with needle 102 mm in length. Needles of No. 18
making certain that the two glass sections touch. A 30 mm 6 gauge, 20 gauge, or 22 gauge are satisfactory.
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D1319 − 20a
6.6 Regulator(s), capable of adjusting and maintaining the 3000000982.
pressure within the 0 kPa to 103 kPa delivery range. Current production of batches of the dyed gel will have lot
numbers starting with 3000000983.
7. Reagents and Materials 7.2.1.1 In 2019, UOP LLC obtained a new supplier for the
7.1 Silica Gel,4 manufactured to conform to the specifica- missing component of the Fluorescent Indicator Dyed Gel and
tions shown in Table 2. To be suitable for use, dry the gel in a produced a prototype version (Lot # 3000000983) of the dyed
shallow vessel at 175 °C for 3 h. Transfer the dried gel to an air gel for evaluation. A performance evaluation (see Appendix
tight container while still hot, and protect it thereafter from X1) to compare multiple batches of original (legacy) dyed gel
atmospheric moisture. to the prototype was conducted and the data indicates that all
the dyed gels demonstrated similar reproducibility. Biases in
NOTE 2—Some batches of silica gel that otherwise meet specifications the order of magnitude of repeatability were determined with
have been found to produce olefin boundary fading. The exact reason for
this phenomenon is unknown but will affect accuracy and precision. aromatics in spark-ignition engine fuels (gasoline) and with
TABLE 2 Silica Gel Specifications aromatics and olefins in aviation turbine fuel. The calculation
Surface area,A m2/g 430 to 530 and reporting sections of the method do not require a bias
pH of 5 % water slurryB 5.5 to 7.0 correction. Where appropriate, consult specification and regu-
Loss on ignition at 955 °C, mass percent 4.5 to 10.0 latory organizations on the use of this method.
Iron content as Fe2O3, dry basis, mass-ppm 50 max
Particle Size 7.3 Isoamyl Alcohol, (3-methyl-1-butanol) 99 %.
Sieve NumberC µm Mass Percent
(Warning—Flammable. Health hazard.)
on 60 250 0.0 max
on 80 180 1.2 max 7.4 Isopropyl Alcohol, (2-propanol) minimum 99 % purity.
on 100 150 5.0 max (Warning—Flammable. Health hazard.)
through 200 75 15.0 max
A
Silica gel surface area determined by Test Method D3663. 7.5 Pressuring Gas—Air (or nitrogen) delivered to the top
B
The pH of the silica gel is determined as follows: Calibrate a pH meter with of the column at pressures controllable over the range from
standard pH 4 and pH 7 buffer solutions. Place 5 g of the gel sample in a 250 mL 0 kPa to 103 kPa gauge. (Warning—Compressed gas under
beaker. Add 100 mL of D.I. water and a stirring bar. Stir the slurry on a magnetic
stirrer for 20 min and then determine the pH with the calibrated meter. high pressure.)
C
Detailed requirements for these sieves are given in Specification E11 and BS
410–1:2000.
7.6 Acetone, reagent grade, residue free. (Warning—
Flammable. Health hazard.)
7.2 Fluorescent Indicator Dyed Gel—A standard dyed gel,
4,5 7.7 Buffer Solutions, pH 4 and 7.
consisting of a mixture of recrystallized Petrol Red AB4 and
purified portions of the olefin and aromatic dyes obtained by 8. Sampling
chromatographic adsorption, following a definite, uniform
procedure, and deposited on silica gel. The dyed gel shall be 8.1 Obtain a representative sample in accordance with
stored in a dark place under an atmosphere of nitrogen. When sampling procedures in Practice D4057. For samples that
stored under these conditions, the dyed gel can have a shelf life would meet volatility conditions of Group 2 or less of Test
of at least five years. It is recommended that portions of the Method D86, ensure that the sample is maintained at a
dyed gel be transferred as required to a smaller working vial temperature of ≤4 °C when opening or transferring the sample.
from which the dyed gel is routinely taken for analyses. (Warning—Flammable. Health hazard.)
7.2.1 Early in 2018, a key component of the Fluorescent
9. Preparation of Apparatus
Indicator Dyed Gel became unavailable. An alternative dye
was substituted, but the reformulated dyed gel was later found 9.1 Mount the apparatus assembly in a darkened room or
to be unsuitable for the analysis of aviation turbine fuel, diesel area to facilitate observation of zone boundaries. For multiple
fuel, and gasoline samples (spark-ignition engine fuels). Al- determinations, assemble an apparatus that includes the ultra-
though UOP LLC, the listed sole source supply of the dyed gel, violet light source, a rack to hold the columns, and a gas
suspended manufacture and sale of the Fluorescent Indicator manifold system providing a connection to the desired number
Dyed Gel upon learning of this issue, six lots of the reformu- of columns.
lated dyed gel had already been distributed and two lots were
not made commercially available. In analyzing any sample 10. Procedure
type by Test Method D1319, users shall not report results 10.1 Ensure that the silica gel is tightly packed in the
obtained using any of the following lot numbers of Fluorescent column and charger section (up to the appropriate level), which
Indicator Dyed Gel: 3000000975, 3000000976, 3000000977, includes the appropriate amount of dyed gel (3 mm to 5 mm)
3000000978, 3000000979, 3000000980, 3000000981, and added to an approximately half-full separator section, prior to
the start of the sample analysis. See Note 3 for specific
guidance.
4
If you are aware of alternative suppliers, please provide this information to
ASTM International Headquarters. Your comments will receive careful consider- NOTE 3—One way to prepare the column for analysis is to freely
ation at a meeting of the responsible technical committee,1 which you may attend. suspend the column from a loose-fitting clamp placed immediately below
5
The sole source of supply of the standard dyed gel known to the committee at the pressuring gas connection of the charger section. While vibrating the
this time is produced by UOP LLC, and distributed by Advanced Specialty Gas column along its entire length, add small increments of silica gel through
Equipment Inc, 241 Lackland Drive, Middlesex, New Jersey 08846. Request “FIA a glass funnel into the charger section until the separator section is half
Standard Dyed Gel,” UOP LLC Product No. 80675. full. Stop the vibrator and add a 3 mm to 5 mm layer of dyed gel. Start the
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D1319 − 20a
vibrator and vibrate the column while adding additional silica gel.
Continue to add silica gel until the tightly packed gel extends approxi-
mately 75 mm into the charger section. Wipe the length of the column
with a damp cloth while vibrating the column. This aids in packing the
column by removing static electricity. Vibrate the column after filling is
completed for at least 4 min. More than one column can be prepared
simultaneously by mounting several on a frame or rack to which an
electric vibrator is attached.
10.2 Attach the filled column to the apparatus assembly in
the darkened room or area, and when a permanently mounted
meter rule is used, fasten the lower end of the column to the
fixed rule.
10.3 For samples that would meet volatility conditions of
Group 2 or less of Test Method D86, chill the sample and a
hypodermic syringe to less than 4 °C. Draw 0.75 mL 6
0.03 mL of sample into the syringe and inject the sample
approximately 30 mm below the surface of the gel in the
charger section.
10.4 Fill the charger section to the spherical joint with
isopropyl alcohol. Connect the column to the gas manifold and
apply 14 kPa 6 2 kPa gas pressure for 2.5 min 6 0.5 min to FIG. 3 Pictorial Aid for Identification of Chromatographic Bound-
move the liquid front down the column. Increase the pressure aries
to 34 kPa 6 2 kPa gauge for another 2.5 min 6 0.5 min and
then adjust the pressure required to give a transit time of about
1 h. Usually a gas pressure of 28 kPa to 69 kPa gauge is needed
for gasoline-type samples and 69 kPa to 103 kPa gauge for jet
fuels. The pressure required will depend on the tightness of
packing of the gel and the molecular weight of the sample. A
transit time of 1 h is optimum; however, high-molecular weight
samples may require longer transit times.
10.5 After the red, alcohol-aromatic boundary has advanced
approximately 350 mm into the analyzer section, make a set of
readings by quickly marking the boundary of each hydrocarbon
zone observed in ultraviolet light in the following sequence.
(Warning—Direct exposure to ultraviolet light can be
harmful, and operators should avoid this as much as possible,
particularly with regard to their eyes.) For the noninfluorescent
saturate zone, mark the front of the charge and the point where
the yellow fluorescence first reaches its maximum intensity; for
the upper end of the second, or olefin zone, mark the point
where the first intense blue fluorescence occurs; finally, for the
upper end of the third, or aromatic zone, mark the upper end of
the first reddish or brown zone. Refer to Fig. 3 as an aid in
identifying the boundaries. With colorless distillates, the
alcohol-aromatic boundary is clearly defined by a red ring of
FIG. 4 Pictorial Aid for Identification of Chromatographic Bound-
dye. However, impurities in cracked fuels often obscure this aries of Oxygenate Blended Fuel Samples
red ring and give a brown coloration, which varies in length,
but which shall be counted as a part of the aromatic zone,
except that when no blue fluorescence is present, the brown or
reddish ring shall be considered as part of the next distinguish- 10.6 When the sample has advanced at least another 50 mm
able zone below it in the column. With some oxygenate down the column, make a second set of readings by marking
blended fuel samples, another red band may appear several the zones in the reverse order as described in 10.5 so as to
centimetres above the reddish or brown alcohol-aromatic minimize errors due to the advancement of boundary positions
boundary (see Fig. 4) and shall be ignored. Avoid touching the during readings. If the marking has been made with a glass-
column with the hands while marking the zones. If the writing pencil, two colors can be used to mark off each set of
boundaries have been marked off with index clips, record the measurements and the distances measured at the end of the test
measurements. with the analyzer section lying horizontally on the bench top.
NOTE 4—The first maximum intense yellow fluorescence is defined to If the boundaries have been marked off with index clips, record
be the center of the lowest intense yellow fluorescent band. the measurements.
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D1319 − 20a
10.7 Erroneous results can be caused by improper packing 12. Report
of the gel or incomplete elution of hydrocarbons by the 12.1 For samples that are composed exclusively of hydro-
alcohol. With precision bore columns, incomplete elution can carbons (that is, oxygenate-free samples) report the averaged
be detected from the total length of the several zones, which value for each hydrocarbon type to the nearest 0.1 % by
must be at least 500 mm for a satisfactory analysis. With volume as calculated in Eq 1-3.
standard wall tubing, this criterion of total sample length is not
12.2 For samples that contain oxygenated blending
strictly applicable because the inside diameter of the analyzer
components, report the averaged value for each hydrocarbon
section is not the same in all columns.
type corrected to a total sample basis (C') to the nearest 0.1 %
NOTE 5—For samples containing substantial amounts of material by volume as determined in Eq 4. Since the total volume
boiling above 204 °C, the use of isoamyl alcohol instead of isopropyl percent oxygenates in the sample is neither measured nor
alcohol may improve elution. calculated by Test Method D1319, but rather determined by
10.8 Release the gas pressure and disconnect the column. To Test Method D4815 and D5599 or equivalent (see variable B in
remove used gel from the precision bore column, invert it Eq 4), it is not necessary to report the total volume percent
above a sink and insert through the wide end a long piece of oxygenates concentration by Test Method D1319.
No. 19 gauge hypodermic tubing with a 45° angle tip. By 13. Precision and Bias6
means of 6 mm outside diameter copper tubing at the opposite
13.1 The following criteria are to be used for judging the
end for attaching a rubber tube, connect to a water tap and flush
acceptability of results (95 % probability):
with a rapid stream of water. Rinse with residue-free acetone
and dry by evacuation. 6
Supporting data regarding the precision obtained from a round robin test for
oxygenate and non-oxygenated containing automotive spark-ignition engine fuels
11. Calculation samples in Table 4 have been filed at ASTM International Headquarters and may be
obtained by requesting Research Report RR:D02-1361. Contact ASTM Customer
11.1 For each set of observations calculate the hydrocarbon Service at service@astm.org.
types to the nearest 0.1 % by volume as follows:
TABLE 3 Reproducibility and Repeatability–Oxygenate Free
Aromatics, percent volume 5 ~ L a /L ! 3 100 (1)
Samples
Olefins, percent volume 5 ~ L o /L ! 3 100 (2) Volume Percent
Saturates, percent volume 5 ~ L s /L ! 3 100 (3) Level Repeatability Reproducibility
Aromatics 5 0.7 1.5
where: 15 1.2 2.5
La = length of the aromatic zone, mm, 25 1.4 3.0
35 1.5 3.3
Lo = length of the olefin zone, mm, 45 1.6 3.5
Ls = length of the saturate zone, mm, and 50 1.6 3.5
L = sum of La + Lo + Ls. 55 1.6 3.5
65 1.5 3.3
Average the respective calculated values for each type and 75 1.4 3.0
85 1.2 2.5
report as directed in 12.1. If necessary, adjust the result for the 95 0.7 1.5
largest component so that the sum of the components is 100 %. 99 0.3 0.7
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D1319 − 20a
13.1.1 Repeatability—The difference between successive 13.1.4 Table 4 shall be used for judging the repeatability and
test results, obtained by the same operator with the same reproducibility of oxygenate and non-oxygenate containing
apparatus under constant operating conditions on identical test automotive spark-ignition engine fuels (gasolines) over the
material would, in the long run, in the normal and correct specified concentration ranges. Non-oxygenated automotive
operation of the test method, exceed the values in Table 3 or spark-ignition fuels outside the valid test result for reporting
Table 4 only in one case in twenty. concentration range indicated in Table 4 may use the precision
in Table 3 within its applicable concentration ranges.
TABLE 4 Reproducibility and Repeatability for Oxygenated and 13.2 Bias—Bias cannot be determined because there are no
Non-Oxygenated Spark-Ignition Engine Fuels6 acceptable reference materials suitable for determining the bias
Inclusive Valid Test for the procedure in this test method.
Result Range in Repeatability,
Reproducibility
Volume Percent Volume Percent NOTE 6—The precision specified in Table 4 was determined with
(see Table 5) automotive spark ignition engine fuels that contained oxygenated blending
Aromatics 9.3 to 43.7 1.3 3.7 components as well as fuels that did not contain oxygenated components.6
OlefinsA,B 2.1 to 39.7 0.26X0.6 0.82X0.6 Test Methods D4815 and D5599 were both used to determine oxygenates
Saturates 40.8 to 72.2 1.5 4.2 in the interlaboratory study for precision listed in Table 4. EPA has
A
X = the average of two results in volume percent of the hydrocarbon type; each replaced its GC/OFID procedure with Test Method D5599.
result is to be within the ranges in Table 5. 13.3 Relative Bias—A relative bias assessment of Test
B
Several examples calculated for volume percent of olefins from exponential
equations listed in Table 4: Method D1319 versus Test Method D5769 for the determina-
tion of total aromatics in spark-ignition engine fuel was
Level Repeatability Reproducibility conducted using data from the ASTM D02 Interlaboratory
4.0 0.6 1.9 Crosscheck Program. The assessment was performed in accor-
10.0 1.0 3.3
20.0 1.6 4.9
dance with the requirements of Practice D6708 with a
30.0 2.0 6.3 successful outcome. It was based on measurements of total
33.0 2.1 6.6 aromatics in spark-ignition engine fuels supplied to the ASTM
Proficiency Test Program by participating laboratories between
February 2007 and October 2014 and is documented in
13.1.2 Reproducibility—The difference between two single Research Report RR:D02-1813.7
and independent results, obtained by different operators work-
NOTE 7—In the United States, the EPA requires the measurement of
ing in different laboratories on identical test material would, in total aromatics in spark-ignition engine fuels by Test Method D5769.
the long run, in the normal and correct operation of the test Effective Jan. 1, 2016, there is an allowance in the regulation to use other
method, exceed the values in Table 3 or Table 4 only in one test methods if they are formally correlated with the specified test method
case in twenty. by a consensus organization, for example, ASTM. This relative bias
statement is intended to satisfy the requirement and allow use of Test
13.1.3 Table 3 shall be used for judging repeatability and Method D1319 bias-corrected results in the stated concentration ranges in
reproducibility of fuel samples that do not contain oxygenated place of Test Method D5769 for total aromatics content.
blending components and with a final boiling point of <315 °C.
13.3.1 The degree of agreement between results from Test
It is applicable over the specified test method working and
Method D1319 and Test Method D5769 can be further im-
corresponding valid test result concentration ranges. Table 3
proved by applying correlation equation (Eq 5 or Eq 6)
should not be used for spark-ignition engine fuels (gasolines)
unless the fuel is outside of the specified valid test result for 7
Supporting data have been filed at ASTM International Headquarters and may
reporting concentration ranges of Table 4 and does not contain be obtained by requesting Research Report RR:D02-1813. Contact ASTM Customer
oxygenates. Service at service@astm.org.
Total olefins Table 4 valid test result 4 33 1.9 6.7 2.1 to 39.7
reporting range
Total saturates Table 4 valid test result 45 68 4.2 4.2 40.8 to 72.2
reporting range
A
Method working range:
• high expected concentration limit – estimated using highest ILS sample mean
• low expected concentration limit – estimated using lowest ILS sample mean
B
Valid test result range: due to testing variation, results within this range inclusively are considered valid for reporting and for applying the precision (R and r) functions:
• high limit: highest ILS sample mean + Rhighest ILS sample mean (per D6300)
• low limit: lowest ILS sample mean – Rlowest ILS sample mean (per D6300)
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D1319 − 20a
(Research Report RR:D02-1813),7 and this correlation equa- 13.3.2.1 The correlation equation is only applicable for
tion shall be utilized when reporting compliance with EPA fuels in the stated concentration range from 3.3 % to 34.4 % by
fuels program. Sample-specific bias, as defined in Practice volume as reported by Test Method D1319 and T95 from
D6708, was observed for some samples after applying the 149.1 °C to 196.6 °C (300.3 °F to 385.8 °F) as reported by Test
bias-correction for the material types and property range listed Method D86.
below. 13.3.2.2 The correlation equation is applicable for fuels that
13.3.2 Correlation Equation: when determined by Test Method D5769 are in the concentra-
Predicted Test Method D5769 = tion range of 3.7 % to 29.4 % by volume and T95 from
bias-corrected Test Method D1319 = 149.1 °C to 196.6 °C (300.3 °F to 385.8 °F) as reported by Test
0.969 3 C D1319 2 @ 0.0986 3 ~ T 95 2 171.4! # (5) Method D86.
for T95 expressed in degrees Celsius, or
NOTE 8—The Test Method D5769 concentration range used to develop
Predicted Test Method D5769 = the Practice D6708 assessment may not cover the entire scope indicated in
bias-corrected Test Method D1319 = the scope of Test Method D5769 for total aromatics
0.969 3 C D1319 2 @ 0.0548 3 ~ T 95 2 340.6! # (6) NOTE 9—The correlation equation was developed from a variety of fuel
for T95 expressed in degrees Fahrenheit. samples from the ASTM Interlaboratory Crosscheck programs; however,
it is recommended that the correlation equation be verified for samples of
where: interest to ensure applicability.
CD1319 = volume percent as reported by Test Method D1319,
and 14. Keywords
T95 = distillation temperature at which 95 % of the 14.1 aromatics; fluorescent indicator adsorption (FIA); hy-
sample has evaporated when tested in accordance drocarbon types; olefins; saturates
with Test Method D86.
APPENDIX
(Nonmandatory Information)
X1.1 Background—In 2019, UOP LLC obtained a new X1.2.2 Subjective Evaluation—Laboratories provided an as-
supplier for the missing component of the Fluorescent Indica- sessment of the prototype dyed gel compared to their original
tor Dyed Gel and produced a prototype version (Lot # (legacy) dyed gel in terms of color and how distinct the
3000000983) of the dyed gel for evaluation. In 2019, a boundaries are from one zone to another.
performance evaluation was conducted to compare multiple
batches of the original (legacy) dyed gel to the prototype. The X1.3 Discussion of Results—The samples were analyzed
results and observations are documented below.8 side-by-side in order to compare the color and distinctiveness
of regions produced by the two dyed gels (original v. proto-
X1.2 Protocol—The study was to evaluate the dyed gels type). The olefins zone color for aviation turbine fuels was
from an objective (results) and subjective (efficacy of fluores- found to be fainter with the prototype dyed gel, resulting in a
cence for olefins and aromatics compounds) point of view. The slightly lower, but statistically significant, olefin result on
study included ten laboratories analyzing twelve gasoline average, and a slightly higher average aromatic result. No
(spark-ignition engine fuel), twelve aviation turbine fuels, and biases were observed for saturates in aviation turbine fuel or
three diesel fuel samples. The three diesel fuels were not for saturates and olefins in the gasoline (spark-ignition engine
included in the statistical evaluation due to insufficient data. fuel) samples. A slight bias was observed for the aromatics in
The final data was evaluated statistically using Practice D6708. spark-ignition engine fuels. The bias is within the repeatability
X1.2.1 Objective Evaluation—Laboratories performed the stated in Table 3 and Table 4. Reproducibility (R) also was
analysis of samples side-by-side to capture any notable differ- compared between the dyed gels and found to be similar for all
ences in the analytical length, or time between the prototype fuel types and component combinations with the exception of
dyed gel and their original (legacy) dyed gel. Analysis was the very low olefin contents in aviation turbine fuels, which
performed according to Test Method D1319 without deviation. was statistically significantly more variable with the original
Results were reported as volume percent saturates, aromatics, (legacy) dye. Table X1.1 summarizes the statistical outcome of
and olefins. the study using Practice D6708 techniques.
X1.3.1 It is understood that formal precision and bias
8
cannot be determined due to the design of the study as
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-2005. Contact ASTM Customer side-by-side analysis of the samples was necessary for a
Service at service@astm.org. subjective evaluation of the prototype dyed gel. There are plans
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D1319 − 20a
TABLE X1.1 Summary of Precision Analyses
Hydrocarbon Type Fuel Concentration Range Dye Bias Assessment (D6708) Outcomes
Saturates Gasoline 47.7 % – 84.3 % Legacy No bias correction, no sample-specific biases
Saturates Gasoline 47.6 % – 84.2 % Proto
Saturates Jet 77.1 % – 84.1 % Legacy No bias correction, no sample-specific biases
Saturates Jet 76.9 % – 84.3 % Proto
Olefins Gasoline 1.1 % – 36.7 % Legacy No bias correction, no sample-specific biases
Olefins Gasoline 1.1 % – 36.3 % Proto
Olefins Jet 0.7 % – 1.0 % Legacy Fail—inadequate variation among samples,
Olefins Jet 1.1 % – 1.6 % Proto but abbreviated analysis indicates L = P + 0.4
Aromatics Gasoline 12.0 % – 46.5 % Legacy L = 1.02 P – 0.74, no sample-specific biases
Aromatics Gasoline 12.4 % – 46.7 % Proto
Aromatics Jet 14.6 % – 21.4 % Legacy L = P – 0.3, no sample-specific biases
Aromatics Jet 14.8 % – 22.3 % Proto
to conduct a formal ILS for updating the test method precision X1.3.1.2 Example 2 with Aviation Turbine Fuels—Olefins
for spark-ignition engine fuels and aviation turbine fuels using with concentrations of 0.7 % to 1.6 % showed a bias of 0.4 %.
a combination of the prototype dyed gel with current and future This bias is equal or less than the repeatability stated in Table
batches of dyed gels once such batches are in commercial use. 3 (for example r = 0.4 at 1 % by volume).
There was a bias determined between the two dyes with certain X1.3.1.3 Example 2a with Aviation Fuels—Aromatics with
hydrocarbon types. Below are examples of hydrocarbon types concentrations of 14.6 % to 22.3 % showed a bias of 0.3 %.
and the relative bias expected using Table X1.1. The degree of This bias is less than the repeatability stated in Table 3 (for
bias observed is less than repeatability of each hydrocarbon
example, r = 1.2 to 1.4 approximately).
type.
X1.3.1.1 Example 1 with Spark Ignition Fuels (Gasoline)— NOTE X1.1—Diesel fuels were not included in the bias assessment
Aromatics with concentrations of the range 12.0 % to 46.7 % because of limited number of samples in the study (three). In addition,
by volume showed an absolute bias of 0.5 % by volume at the most diesel fuels are outside the current scope of Test Method D1319 with
lower range to 0.2 % by volume at the upper range, respec- a FBP limit of <315 °C (599 °F) and such inclusion in the method would
require additional studies.
tively. This bias is less than the repeatability stated in Tables 3
and 4 of published Test Method D1319 (for example, r = 1 –
1.6 in Table 3 and r = 1.3 in Table 4 for spark ignition only).
SUMMARY OF CHANGES
Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D1319 – 20) that may impact the use of this standard. (Approved August 1, 2020.)
Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D1319 – 19) that may impact the use of this standard. (Approved July 15, 2020.)
(1) Revised subsections 1.1, 1.5, and 13.1.3. (5) Added Table 5.
(2) Added new subsections 1.3, 1.5.1, 1.5.2, 1.5.3, and 13.1.4. (6) Revised Footnote 7.
(3) Added definition for gasoline in subsection 3.1.2. (7) Revised Note 6.
(4) Revised Table 4.
Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D1319 – 18) that may impact the use of this standard. (Approved Aug. 1, 2019.)
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D1319 − 20a
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